Abstract
Understanding the ways in which the constituents of ionic liquids, i.e. the type of cation, its substitution, and the type of anion chosen, interact with reactants is prerequisite to deliberately designing an ionic liquid solvent with optimum performance. Several approaches, including physico-chemical and spectroscopic measurements and computational studies of binary ionic liquid-substrate mixtures have been presented that investigate the strength of interactions.
The qualitative order of the basicity (hydrogen bond acceptor potential) of anions as most prominent force is already reasonably well understood, and reliably determined using, e.g. selective solvatochromic dyes. In certain reactions, the relative order of basicity correlates well with the reactivity of substrates. However, the determination of a relative order for the cations is still in its infancy. Owing to the fact that potential cation-derived interactions may not solely be due to hydrogen bond interactions, but also to ion pair interactions (electron pair donor/acceptor properties), the relative magnitudes of interactions between the anion and cation vary considerably – even in the absence of solutes – depending on the experimental method. In addition, it appears that the basicity of the anion superimposes in many instances on the effects exhibited by the cation and/or the cation’s substituent. Hence, understanding the effect of the cation on the activation of substrates is still a challenge.
This chapter aims at summarising the trends observed for binary model systems in experimental and computational investigations, and drawing conclusions about ionic liquid structure-induced effects relevant to organic reactions, in particular nucleophilic substitution reactions.
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References
Tobias DJ, Hemminger JC (2008) Science 319:1197–1198
Seddon RS (1999) Ionic liquids: designer solvents? In: Boghosian S, Dracopoulos V, Kontoyannis CG, Voyiatzis GA (eds) The International George Papatheodorou Symposium, Institute of Chemical Engineering and High Temperature Chemical Processes, Patras, pp 131–135
Freemantle M (1998) Chem Eng News 76(13):32–37
Reichardt Ch (2003) Solvents and solvent effects in organic chemistry, 3rd edn. Wiley, Weinheim
Abraham MH, Zissimos AM, Huddleston JG, Willauer HD, Rogers RD, Acree WE (2003) Ind Eng Chem Res 42:413–418
Dimroth K, Reichardt Ch, Siepmann T, Bohlmann F (1963) Liebigs Ann Chem 661:1–37
Carmichael AJ, Seddon KR (2000) J Phys Org Chem 13:591–595
Fletcher KA, Storey IA, Hendricks AE, Pandey S, Pandey S (2001) Green Chem 3:210–215
Aki SNVK, Brennecke JF, Samanta A (2001) Chem Commun 413–414
Muldoon MJ, Gordon GM, Dunkin IR (2001) J Chem Soc Perkin Trans 2433–435
Baker SN, Baker GA, Bright FV (2002) Green Chem 4:165–169
Poole CF (2004) J Chrom A 1037:49–82
Reichardt Ch (2005) Green Chem 7:339–351
Crowhurst L, Mawdsley PR, Perez-Arlandis JM, Salter PA, Welton T (2003) Phys Chem Chem Phys 5:2790–2794
Oehlke A, Hofmann K, Spange S (2006) New J Chem 30:533–636
Fukaya Y, Sugimoto A, Ohno H (2006) Biomacromol 3295–3297
Lungwitz R, Spange S (2008) New J Chem 32:392–394
Fukaya Y, Hayashi K, Wada M, Ohno H (2008) Green Chem 10:44–46
Lungwitz R, Friedrich M, Linert W, Spange S (2008) New J Chem 32:1457–1644
Fujisawa T, Fukuda M, Terazima M, Kimura Y (2006) J Phys Chem A 110:6164–6172
Kamlet MJ, Taft RW (1976) J Am Chem Soc 98:377–383
Taft RW, Kamlet MJ (1976) J Am Chem Soc 98:2886–2894
Kamlet MJ, Abboud JL, Taft RW (1977) J Am Chem Soc 99:6027–6038
Wakai C, Oleinikova A, Ott M, Weingärtner H (2005) J Phys Chem B 109:17028–17030
Weingärtner HZ (2006) Z Phys Chem 220:1395–1405
Daguenet C, Dyson PJ, Krossing I, Oleinikova A, Slattery J, Wakai C, Weingärtner H (2006) J Phys Chem B 110:12682–12688
Weingärtner H (2008) Angew Chem 120:664–682
Bini R, Bortolini O, Chiappe C, Pieraccini D, Siciliano T (2007) J Phys Chem B 111:598–604
Bonhôte P, Dias AP, Papageorgiou N, Kalyanasundaram K, Grätzel M (1996) Inorg Chem 35:1168–1178
Huddleston JG, Visser AE, Reichert WM, Willauer HD, Broker GA, Rogers RD (2001) Green Chem 3:156–164
Deetlefs M, Shara M, Seddon KR (2005) Refractive indices of ionic liquids. In: Rogers RD, Seddon KR (eds) Ionic liquids IIIa: fundamentals, progress, challenges, and opportunities, properties and structure. American Chemical Society, Washington, pp 219–233
Deetlefs M, Seddon KR, Shara M (2006) New J Chem 30:317–326
Koppel IA, Burk P, Koppel I, Leito I, Sonoda T, Mishima M (2000) J Am Chem Soc 122:5114–5124
Seddon KR, Stark A, Torres M-J (2000) Pure Appl Chem 72:2275–2287
Lee SH, Lee SB (2005) Chem Commun 3469–3471
Jin H, O’Hare B, Dong J, Arzhantsev S, Baker GA, Wishart JF, Benesi AJ, Maroncelli M (2008) J Phys Chem B 112:81–92
Earle MJ, Engel BS, Seddon KR (2004) Austr J Chem 57:149–150
Angelini G, Chiappe C, De Maria P, Fontana A, Gasparrini F, Pieraccini D, Pierini M, Siani G (2005) J Org Chem 70:8193–8196
Wasserscheid P, Keim W (2000) Angew Chem Int Ed 39:3772–3789
Brasse CC, Englert U, Salzer A, Waffenschmidt H, Wasserscheid P (2000) Organometallics 19:3818–3823
Wasserscheid P, Gordon CM, Hilgers C, Muldoon MJ, Dunkin IR (2001) Chem Commun 1186–1187
Blanchard LA, Brennecke JF (2001) Ind Eng Chem Res 40:287–292
Favre F, Olivier-Bourbigou H, Commereuc D, Saussine L (2001) Chem Commun 15:1360–1361
Anthony JL, Maginn EJ, Brennecke JF (2001) J Phys Chem B 105:10942–10949
Swatloski RP, Visser AE, Reichert WM, Broker GA, Farina LM, Holbrey JD, Rogers RD (2002) Green Chem 4:81–87
Najdanovic-Visak V, Esperanca JMSS, Rebelo LPN, Nunes da Ponte N, Guedes HJR, Seddon KR, de Souza HC, Szydlowski J (2002) Phys Chem Chem Phys 4:1701–1703
Heintz A, Lehmann JK, Wertz C (2003) J Chem Eng Data 48:472–474
Wu C-T, Marsh KN, Deev AV, Boxall JA (2003) J Chem Eng Data 48:486–491
Najdanovic-Visak V, Esperanca JMSS, Rebelo LPN, da Ponte MN, Guedes HJR, Seddon KR, Szydlowski J (2003) J Phys Chem B 107:12797–12807
Heintz A, Lehmann JK, Verevkin SP (2003) Thermodynamic properties of liquid mixtures containing ionic liquids. In: Rogers RD, Seddon KR (eds) Ionic liquids as green solvents: progress and prospects. American Chemical Society, Washington, pp 134–150
Domanska U, Marciniak A (2003) J Chem Eng Data 48:451–456
Marczak W,Verevkin SP, Heintz A (2003) J Sol Chem 32:519–526
Aki SNVK, Mellein BR, Saurer EM, Brennecke JF (2004) J Phys Chem B 108:20355–20365
Crosthwaite MJ, Aki SNVK, Maginn EJ, Brennecke FJ (2004) J Phys Chem B 108:5113–5119
Ohlin CA, Dyson PJ, Laurenczy G (2004) Chem Commun 1070–1071
Kato R, Krummen M, Gmehling J (2004) Fluid Phase Equil 224:47–54
Stark A, Ajam M, Green M, Raubenheimer HG, Ranwell A, Ondruschka B (2006) Adv Synth Catal 348:1934–1941
Domanska U, Pobudkowska A, Eckert F (2006) Green Chem 8:268–276
Cadena C, Anthony JL, Shah JK, Morrow TI, Brennecke KF, Maginn EJ (2004) J Am Chem Soc 26:5300–5308
Kazarian SG, Briscoe BJ, Welton T (2000) Chem Commun 20:2047–2048
Canongia Lopes JNA, Pádua AAH (2006) J Phys Chem B 110:3330–3335
Canongia Lopes JNA, Costa Gomes MF, Pádua AAH (2006) J Phys Chem B 110:16816–16818
Pádua AAH, Costa Gomes MF, Canongia Lopes JNA (2007) Acc Chem Res 40:1087–1096
Abraham MH (1993) Chem Soc Rev 22:73–83
Abraham MH, Acree WE (2006) Green Chem 8:906–915
Anderson JL, Ding J, Welton T, Armstrong DW (2002) J Am Chem Soc 124:14247–14254
Kato R, Gmehling J (2005) J Chem Thermodyn 37:603–619
Kato R, Gmehling J (2004) Fluid Phase Equil 226:37–44
Kato R, Gmehling J (2005) Fluid Phase Equil 235:124
Heintz A, Casas LM, Nestrerov IA, Emel’yanenko VN, Verevkin SP (2005) J Chem Eng Data 50:1510–1514
Heintz A, Verevkin SP (2005) J Chem Eng Data 50:1515–1519
Letcher TM, Marciniak A, Marciniak M, Domanska U (2005) J Chem Eng Data 50:1294–1298
Krummen M, Gruber D, Gmehling J (2000) Ind Eng Chem Res 93:2114–2123
Braun O (2007) Zur Beziehung zwischen Struktur und Lösungsmitteleigenschaften von ionischen Flüssigkeiten mittels Headspace-Gaschromatographie (Regarding the structure-solvent property relationship of ionic liquids investigated by headspace gas chromatography). Dissertation, Institute for Technical Chemistry and Environmental Chemistry, Friedrich-Schiller University Jena, Germany
Latscha HP, Schilling G, Klein HA (1990) Chemie – Datensammlung. Springer, Berlin Heidelberg New York
Lide DL (2002) Handbook of chemistry and physics. CRC, Boca Raton
Hachenberg H, Beringer K (1996) Die Headspace-Gaschromatographie als Analysen- und Meßmethode. Vieweg Verlag, Braunschweig
Kosmulski M, Gustafsson J, Rosenholm JB (2004) Thermochim Acta 412:47–53
Baranyai KJ, Deacon GB, MacFarlane DR, Pringle JM, Scott JL (2004) Aust J Chem 57:145–147
Beste Y, Eggersmann M, Schoenmakers H (2005) Chem Ing Tech 77:1800–1808
Selvan MS, McKinley MD, Dubois RH, Atwood JL (2000) J Chem Eng Data 45:841–845
Gmehling J, Krummen M (to Carl v. Ossietzky University Oldenburg), DE10154052 Separation of aromatic hydrocarbons from non-aromatic hydrocarbons, comprises using a selective solvent selected from liquid onium salts publication date: 2003-07-10
Jork C, Kristen C, Pieraccini D, Stark A, Chiappe C, Beste YA, Arlt W (2005) J Chem Thermodyn 37:537–558
Acre A, Rodriguez O, Soto A (2004) J Chem Eng Data 49:514–517
Liu F, Jiang Y (2007) J Chrom A 1167:116–119
Koch P, Kuesters E (to Novartis Corporate Intellectual Property), WO2004013612 Analytical process 2004-02-12
Foco GM, Bottini SB, Quezada N, de la Fuente JC, Peters CJ (2006) J Chem Eng Data 51:1088–1091
Zhou Q, Wang LS (2006) J Chem Eng Data 51:1698–1701
Zhou Q, Wang LS, Wu JS, Li MY (2007) J Chem Eng Data 52:131–134
Heintz A, Verevkin SP, Ondo D (2006) J Chem Eng Data 51:434–437
Letcher TM, Marciniak A, Marciniak M, Domanska U (2005) J Chem Thermodyn 37:1327–1331
Sellin M, Ondruschka B, Balensiefer T, D’Andola G, Massonne K, Stark A (2008) in preparation
Avent AG, Chaloner PA, Cay MP, Seddon KR, Welton T (1994) J Chem Soc Dalton Trans 3405–3413
Huang J, Chen P, Sun I, Wang SP (2001) Inorg Chim Acta 320:7–11
Headley AD, Jackson NM (2002) J Phys Org Chem 15:52–55
Mele A, Tran CD, De Paoli SH (2003) Angew Chem Int Ed 42:4364–4366
Lin S, Ding M, Chang C, Lue S (2004) Tetrahedron 60:9441–9446
Tubbs JD, Hoffmann MMJ (2004) J Sol Chem 33:379–392
Headley AD, Kotti SRSS, Nam J, Li K (2005) J Phys Org Chem 18:1018–1022
Consorti CS, Suarez PAZ, De Souza RF, Burrow RA, Farrar DH, Lough AJ, Loh W, Da Silva LHM, Dupont J (2005) J Phys Chem B 109:4341–4349
Mele A, Romano G, Giannone M, Ragg E, Fronza G, Raos G, Maron V (2006) Angew Chem Int Ed 45:1123–1126
Singh T, Kumar A (2007) J Phys Chem B 111:7843–7851
Palomar J, Ferro VR, Gilarranz MA, Rodriguez JJ (2007) J Phys Chem B 111:168–180
Daguenet C, Dyson PJ (2007) Inorg Chem 46:403–408
Atwood JL, Atwood JD (1976) Non-stoichiometric liquid enclosure compounds (‘Liquid Clathrates’) In: King B (ed) Inorganic compounds with unusual properties. American Chemical Society, Washintgton, 112–127
Holbrey JD, Reichert WM, Nieuwenhuyzen M, Sheppard O, Hardacre C, Rogers RD (2003) Chem Commun 476–477
Harper JB, Lynden-Bell RM (2004) Mol Phys 102:85–94
Deetlefs M, Hardacre C, Nieuwenhuyzen M, Sheppard O, Soper AK (2005) J Phys Chem B 109:1593–1598
Hardacre C, Holbrey JD, Nieuwenhuyzen M, Youngs TGA (2007) Acc Chem Res 40:1146–1155
Tran CD, Lacerda SHD, Oliveira D (2003) Appl Spectr 57:152–157
Schröder U, Wadhawan JD, Compton RG, Marken F, Suarez PAZ, Consorti C, de Souza RF, Dupont J (2000) New J Chem 24:1009–1015
Cammarata L, Kazarian SG, Salter PA, Welton T (2001) Phys Chem Chem Phys 3:5192–5200
Hanke CG, Lynden-Bell RM (2003) J Phys Chem B 107:10873–10878
Hayashi S, Ozawa R, Hamaguchi H (2003) Chem Lett 32:498–499
Saha S, Hayashi S, Kobayashi A, Hamaguchi H (2003) Chem Lett 32:740–741
Holbrey JD, Reichert WM, Nieuwenhuyzen M, Johnston S, Seddon KR, Rogers RD (2003) Chem Commun 1636–1637
Ozawa R, Hayashi S, Saha S, Kobazashi A, Hamaguchi H (2003) Chem Lett. 32:948–949
Rodríguez H, Brennecke JF (2006) J Chem Eng Data 51:2145–2155
Gómez E, González B, Domínguez Á, Tojo E, Tojo J (2006) J Chem Eng Data 51:696–701
Pires RM, Costa HF, Ferreira AGM, Fonseca IMA (2007) J Chem Eng Data 52:1240–1245
Acre A, Soto A, Ortega J, Sabater G (2008) J Chem Eng Data 53:770–775
MacFarlane DR, Forsyth SA (2003) Acids and bases in ionic liquids. In: Rogers RD, Seddon KR (eds) Ionic liquids as green solvents: progress and prospects. American Chemical Society, Washington, pp 264–276
Thomazeau C, Olivier-Bourbigou H, Magna L, Luts S, Gilbert B (2003) J Am Chem Soc 125:5264–5265
Izgorodina EI, Forsyth M, MacFarlane DR (2007) Aust J Chem 60:15–20
Del Pópolo MG, Kohanoff J, Lynden-Bell RM (2006) J Phys Chem B 110:8798–8803
Del Pópolo MG, Kohanoff J, Lynden-Bell RM, Pinilla C (2006) Acc Chem Res 40:1156–1164
Earle MJ, Katdare SP, Seddon KR (2004) Org Lett 6:707–710
Lancaster NL, Llopis-Mestre V (2003) Chem Commun 2812–2813
Stark A, Seddon KR (2007) Ionic liquids. In: Seidel A (ed) Kirk-Othmer Encyclopaedia of chemical technology, 5th edn. Wiley, Hoboken, pp 836–920
Šebesta R, Kmentová I, Toma Š (2008) Green Chem 10:484–496
Wasserscheid P, Bösmann A, Bolm C (2002) Chem Commun 200–201
Pégot B, Vo-Thanh G, Gori D, Loupy A (2004) Tetrahedron Lett 45:6425–6428
Luo S, Mi X, Zhang L, Liu S, Xu H, Cheng J-P (2006) Angew Chem Int Ed 45:3093–3097
Earle MJ, McCormac PB, Seddon KR (1999) Green Chem 1:23–25
Fukomoto K, Ohno H (2006) Chem Commun 3081–3083
Machado MY, Dorta R (2005) Synthesis 2473–2475
Gausepohl R, Buskens P, Kleinen J, Bruckmann A, Lehmann CW, Klankermayer J, Leitner W (2006) Angew Chem Int Ed 45:3689–3692
Machado MY, Dorta R (2005) Synthesis 2473–2475
Schulz PS, Müller N, Bösmann A, Wasserscheid P (2007) Angew Chem Int Ed 46:1293–1295
Farmer V, Welton T (2002) Green Chem 4:97–102
Seddon KR, Stark A (2002) Green Chem 4:119–123
Aggarwal A, Lancaster NL, Sethi AR, Welton T (2002) Green Chem 4:517–520
Nobuoka K, Kitaoka S, Kunimitsu K, Iio M, Harran T, Wakisaka A, Ishikawa Y (2005) J Org Chem 70:10106–10108
Bartsch RA, Dzyuba SV (2003) Polarity variation of room temperature ionic liquids and its influence on a Diels-Alder reaction. In: Rogers RD, Seddon KR (eds) Ionic liquids as green solvents: progress and prospects. American Chemical Society, Washington, pp 289–299
Forsyth SA, MacFarlane DR, Thomson RJ, von Itzstein M (2002) Chem Commun 714–715
MacFarlane DR, Pringle MJ, Johansson KM, Forsyth SA, Forsyth M (2006) Chem Commun 1905–1917
Ingold CK (1969) Structure and mechanism in organic chemistry, 2nd edn. Cornell University Press, Ithaca
Hughes DE, Ingold CK (1935) J Chem Soc 244–251
Lancaster NL, Welton T, Young GB (2001) J Chem Soc Perkin Trans 2 2267–2270
Lancaster NL, Salter PA, Welton T, Young GB (2002) J Org Chem 67:8855–8861
Lancaster LN, Welton T (2004) J Org Chem 69:5986–5992
Crowhurst L, Falcone R, Lancaster NL, Llopis-Mestre V, Welton T (2006) J Org Chem 71:8847–8853
Crowhurst L, Lancaster NL, Pérez-Arlandis JM, Welton T (2004) J Am Chem Soc 126:11549–11555
Newington I, Pérez-Arlandis JM, Welton T (2007) Org Lett 9:5247–5250
Bini R, Chiappe C, Marmugi E, Pieraccini D (2006) Chem Commun 897–899
Daguenet C, Dyson PJ (2006) Organometallics 25:5811–5816
Carmichael AJ, Earle MJ, Holbrey JD, McCormac PB, Seddon KR (1999) Org Lett 7:997–1000
Herrmann WA, Böhm VPW (1999) J Organometal Chem 572:141–145
Calò V, Giannoccaro P, Nacci A, Monopoli A (2002) J Organometal Chem 645:152–157
Fraga-Dubreuil J, Bourahla K, Rahmouni M, Bazureau JP, Hamelin J (2002) Catal Commun 3:185–190
Gui JZ, Cong XH, Liu D, Zhang XT, Hu ZD, Sun ZL (2004) Catal Commun 5:473–477
Zhang ZF, Wu WZ, Han BX, Jiang T, Wang B, Liu ZM (2005) J Phys Chem B 109:16176–16179
Xing HB, Wang T, Zhou ZH, Dai YY (2005) Ind Eng Chem Res 44:4147–4150
Ganeshpure PA, Das J (2007) React Kin Catal Lett 92:69–74
Naydenov D, Bart H-J (2007) Chem Ing Tech 80:137–143
Li X, Eli W (2008) J Mol Catal A Chem 279:159–164
Ganeshpure PA, George G, Das J (2008) J Mol Catal A Chem 289:182–186
Zhu HP, Yang F, Tang J, He MY (2003) Green Chem 5:38–39
Joseph T, Sahoo S, Halligudi SB (2005) J Mol Catal A Chem 234:107–110
Zhang HB, Xu F, Zhou XH, Zhang GY, Wang CX (2007) Green Chem 9:1208–1211
Cole AC, Jensen JL, Ntai I, Tran KLT, Weaver KJ, Forbes DC, Davis JH (2002) J Am Chem Soc 124:5962–5963
Forbes DC, Weaver KJ (2004) J Mol Catal A Chem 214:129–132
Fang D, Zhou XL, Ye ZW, Liu ZL (2006) Ind Eng Chem Res 45:7982–7984
Jiang T, Chang YH, Zhao GY, Han BX, Yang GY (2004) Synth Commun 34:225–230
Izak P, Mateus NMM, Afonso CAM, Crespo JG (2005) Sep Purif Technol 41:141–145
Wells TP, Hallett JP, Williams CK, Welton T (2008) J Org Chem 73:5585–5588
Shi F, Xiong H, Gu Y, Guo S, Deng Y (2003) Chem Commun 1054–1055
Villagrán C, Banks CE, Deetlefs M, Driver G, Pitner WR, Compton RG, Hardacre C (2005) Chloride determination in ionic liquids. In: Rogers RD, Seddon KR (eds) Ionic liquids IIIb: fundamentals, progress, challenges, and opportunities – transformations and processes. American Chemical Society, Washington, pp 244–258
Bogel-Lukasik E, Domanska U (2004) Green Chem 6:299–303
Stark A, Behrend P, Braun O, Müller A, Ranke J, Ondruschka B, Jastorff B (2008) Green Chem 10:1152–1162
Wilkes S, Zaworotko MJ (1992) Chem Commun 965–967
Kirchner B (2009) lonic liquids from theoretical investigations. Top Curr Chem. doi: 10.1007/128_2009_36
Acknowledgements
I would like to thank Prof. Dr. B. Ondruschka for the support granted at the Institute for Technical Chemistry and Environmental Chemistry of the Friedrich-Schiller University Jena. Furthermore, a big thank you to all members of the Ionic Liquids Group, in particular C. Palik, O. Braun, M. Sellin and M. M. Hoffmann (visiting scientist from SUNY Brockport, USA in 2007/08) for their various contributions. The donation of ionic liquid samples (BASF SE, Merck KGaA, Sigma-Aldrich Chemie GmbH) is greatly appreciated. For financial support, I am indebted to the Friedrich-Schiller University (HWP) and the DFG for funding within the Priority Programme SPP 1191 Ionic Liquids.
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Stark, A. (2008). Ionic Liquid Structure-Induced Effects on Organic Reactions. In: Kirchner, B. (eds) Ionic Liquids. Topics in Current Chemistry, vol 290. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2008_43
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